Zn-doped TiO2 (Zn?TiO2) thin films were prepared by the sol?gel method on titanium substrates with heat treatment at different temperatures. The effects of heat treatment temperatures and Zn doping on the structure, p...Zn-doped TiO2 (Zn?TiO2) thin films were prepared by the sol?gel method on titanium substrates with heat treatment at different temperatures. The effects of heat treatment temperatures and Zn doping on the structure, photocathodic protection and photoelectrochemical properties of TiO2 thin films were investigated. It is indicated that the photoelectrical performance of the Zn?TiO2 films is enhanced with the addition of Zn element compared with the pure-TiO2 film and the largest decline by 897 mV in the electrode potential is achieved under 300 °C heat treatment. SEM?EDS analyses show that Zn element is unevenly distributed in Zn?TiO2 films; XRD patterns reveal that the grain size of Zn?TiO2 is smaller than that of pure-TiO2; FTIR results indicate that Zn - O bond forms on Zn?TiO2 surface. Ultraviolet visible absorption spectra prove that Zn?TiO2 shifts to visible light region.Mott?Shottky curves show that the flat-band potential of Zn?TiO2 is more negative and charge carrier density is bigger than that ofpure-TiO2, implying that under the synergy of the width of the space-charge layer, carrier density and flat-band potential, Zn?TiO2 with 300 °C heat treatment displays the best photocathodic protection performance.展开更多
We developed a novel approach for the preparation of N-doped TiO2 photocatalysts by calcining ammonium titanium oxalate at different temperatures. The structures of N-TiO2 were characterized by powder X-ray diffractio...We developed a novel approach for the preparation of N-doped TiO2 photocatalysts by calcining ammonium titanium oxalate at different temperatures. The structures of N-TiO2 were characterized by powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, diffuse reflectance UV-Vis spectroscopy, and scanning electron microscope. The N-doped TiO2 photocatalysts calcined below 700 ℃ are the pure anatase phase but that calcined at 700 ℃ is a mixture of anatase and rutile phases. The doped N locates at the interstitial site of TiO2 which leads to the narrowing of bad gap of pure anatase N-TiO2. Among all photocatalysts, N-TiO2 photocatalysts calcined at 600 and 400 ℃ exhibit the best performance in the photodegradation of methyl orange under the UV light and all-wavelength light illuminations, respectively; however, because of the perfect crystallinity and the existence of anatase-rutile phase junctions, N-TiO2 photocatalyst calcined at 700 ℃ exhibits the highest specific photodegradation rate, i.e., the highest quantum yield, under both the UV light and all-wavelength light illuminations.展开更多
In this paper, SnS_2 nanosheets arrays sandwiched by porous N-doped carbon and TiO_2(TiO_2@SnS_2@N-C) on flexible carbon cloth are prepared and tested as a free-standing anode for high-performance sodium ion batteries...In this paper, SnS_2 nanosheets arrays sandwiched by porous N-doped carbon and TiO_2(TiO_2@SnS_2@N-C) on flexible carbon cloth are prepared and tested as a free-standing anode for high-performance sodium ion batteries. The as-obtained TiO_2@SnS_2@N-C composite delivers a remarkable capacity performance(840 mA h g^(-1) at a current density of 200 mA g^(-1)), excellent rate capability and long-cycling life stability(293 mA h g^(-1) at 1 A g^(-1) after 600 cycles). The excellent electrochemical performance can be attributed to the synergistic effect of each component of the unique hybrid structure, in which the SnS_2 nanosheets with open framworks offer high capacity, while the porous N-doped carbon nanoplates arrays on flexible carbon cloth are able to improve the conductivity and the TiO_2 passivation layer can keep the structure integrity of SnS_2 nanosheets.展开更多
Lithium-sulfur batteries hold promise for next generation batteries due to their high theoretical energy density and low cost.However,the rapid capacity fading caused by the shuttle of polysulfide between two electrod...Lithium-sulfur batteries hold promise for next generation batteries due to their high theoretical energy density and low cost.However,the rapid capacity fading caused by the shuttle of polysulfide between two electrodes severely hinders the practical application of Li-S batteries.To address the issue,we reported a three-dimensional heterostructured TiO2 nanosheets/N-doped carbon(TO/NC),which is coated on a commercial polypro pylene(PP) separator,as an efficient barrier for Li-S batteries.The TO/NC coating layer provides a bipolar chemical adsorption of lithium polysulfides(LiPSs) via TiO2 nanosheets with exposed(001) facets and N-doped carbon,showing high trapping capacity and remarkable electrocatalytic activity for LiPSs.The slurry-bladed carbon black/sulfur cathode with 64 wt% sulfur offers outstanding performance with an initial capacity of 1314 mAh g^-1 at 0.2 C.Over 900 cycles,the cell still maintains the capacity of 448 mA h g^-1 at a 1 C rate with a degradation rate of only 0.055% per cycle.The separator reported in this work holds great promise for the development of high-energy Li-S batteries.展开更多
A systematic study on geometry, electronic structure and vibrational properties of N-doped TiO2 anatase cluster, within the framework of the density functional theory, has been performed in this work. The calculations...A systematic study on geometry, electronic structure and vibrational properties of N-doped TiO2 anatase cluster, within the framework of the density functional theory, has been performed in this work. The calculations confirmed that the most structures in substitutional model consist of a two-coordinate bridge structure and a three-coordinate hollow structure. The calculated results can well explain the red shift in N-doped TiO2 observed in experiments. The study provides an illustration for the N-doped anatase from the viewpoint of chemical bonding theory.展开更多
A novel visible light-active photocatalyst formulation（NdT/OP） was obtained by supporting N-doped TiO2（NdT） particles on up-conversion luminescent organic phosphors（OP）. The photocatalytic activity of such catal...A novel visible light-active photocatalyst formulation（NdT/OP） was obtained by supporting N-doped TiO2（NdT） particles on up-conversion luminescent organic phosphors（OP）. The photocatalytic activity of such catalysts was evaluated for the mineralization process of spiramycin in aqueous solution. The effect of NdT loading in the range 15–60 wt.% on bulk and surface characteristics of NdT/OP catalysts was investigated by several chemicophysical characterization techniques. The photocatalytic performance of NdT/OP catalysts in the removal of spyramicin from aqueous solution was assessed through photocatalytic tests under visible light irradiation. Total organic carbon（TOC） of aqueous solution,and CO and CO2 gas concentrations evolved during the photodegradation were analyzed. A dramatic enhancement of photocatalytic activity of the photostructured visible active NdT/OP catalysts,compared to NdT catalyst,was observed. Only CO2 was detected in gas-phase during visible light irradiation,proving that the photocatalytic process is effective in the mineralization of spiramycin,reaching very high values of TOC removal. The photocatalyst NdT/OP at 30 wt.% of NdT loading showed the highest photocatalytic activity（58%of TOC removed after 180 min irradiation against only 31% removal after 300 min of irradiation of NdT）. We attribute this enhanced activity to the high effectiveness in the utilization of visible light through improved light harvesting and exploiting. OP particles act as ＂photoactive support＂,able to be excited by the external visible light irradiation,and reissue luminescence of wavelength suitable to promote NdT photomineralization activity.展开更多
Multilevel phase-change memory is an attractive technology to increase storage capacity and density owing to its high-speed,scalable and non-volatile characteristics.However,the contradiction between thermal stability...Multilevel phase-change memory is an attractive technology to increase storage capacity and density owing to its high-speed,scalable and non-volatile characteristics.However,the contradiction between thermal stability and operation speed is one of key factors to restrain the development of phase-change memory.Here,N-doped Ge_(2)Sb_(2)Te_(5)-based optoelectronic hybrid memory is proposed to simultaneously implement high thermal stability and ultrafast operation speed.The picosecond laser is adopted to write/erase information based on reversible phase transition characteristics whereas the resistance is detected to perform information readout.Results show that when N content is 27.4 at.%,N-doped Ge_(2)Sb_(2)Te_(5)film possesses high ten-year data retention temperature of 175℃and low resistance drift coefficient of 0.00024 at 85℃,0.00170 at 120℃,and 0.00249 at 150℃,respectively,owing to the formation of Ge–N,Sb–N,and Te–N bonds.The SET/RESET operation speeds of the film reach 520 ps/13 ps.In parallel,the reversible switching cycle of the corresponding device is realized with the resistance ratio of three orders of magnitude.Four-level reversible resistance states induced by various crystallization degrees are also obtained together with low resistance drift coefficients.Therefore,the N-doped Ge_(2)Sb_(2)Te_(5)thin film is a promising phase-change material for ultrafast multilevel optoelectronic hybrid storage.展开更多
In this paper, ultrafine nitrogen-doped TiO2 photocatalyst with enhanced photocatalytic water-splitting properties was successfully fabricated via a solvothermal method. Herein, polyvinylpyrrolidone（PVP） was used as...In this paper, ultrafine nitrogen-doped TiO2 photocatalyst with enhanced photocatalytic water-splitting properties was successfully fabricated via a solvothermal method. Herein, polyvinylpyrrolidone（PVP） was used as both nitrogen source and stabilizer. The enhancement in water-splitting process can be attributed to the doping of element nitrogen, which could supply an intermediate energy level and promote the separation of photo-excited holes and electrons. Moreover, this paper provides a new application of high-molecular polymer to synthesize solar-driven water-splitting photocatalysts.展开更多
ZrO2/TiO2 composite photocatalytic film was produced on the pure titanium substrate using in-situ Zr（OH）4 colloidal particle by the micro-arc oxidation technique and characterized by scanning electron microscope （...ZrO2/TiO2 composite photocatalytic film was produced on the pure titanium substrate using in-situ Zr（OH）4 colloidal particle by the micro-arc oxidation technique and characterized by scanning electron microscope （SEM）, energy dispersive X-ray （EDX）, X-ray diffraction （XRD） and ultraviolet-visible （UV-Vis） spectrophotometer. The composite film shows a lamellar and porous structure which consists of anatase, futile and ZrO2 phases. The optical absorption edge of film is shifted to longer wavelength when ZrO2 is introduced to TiO2. Furthermore, the photocatalytic reaction rate constants of degradation of rhodamine B solution with ZrO2/TiO2 composite film and pure TiO2 film under ultraviolet irradiation are measured as 0.0442 and 0.0186 h 1, respectively.展开更多
A novel WO3-x/TiO2 film as photoanode was synthesized for photoelectrocatalytic（PEC） reduction of CO2 into formic acid（HCOOH）. The films prepared by doctor blade method were characterized with X-ray diffractometer...A novel WO3-x/TiO2 film as photoanode was synthesized for photoelectrocatalytic（PEC） reduction of CO2 into formic acid（HCOOH）. The films prepared by doctor blade method were characterized with X-ray diffractometer（XRD）, scanning electron microscope（SEM） and transmission electron microscope（TEM）. The existence of oxygen vacancies in the WO3-x was confirmed with an X-ray photoelectron spectroscopy（XPS）, and the accurate oxygen index was determined by a modified potentiometric titrimetry method. After 3h of photoelectrocatalytic reduction, the formic acid yield of the WO3-x/TiO2 film is 872 nmol/cm^2, which is 1.83 times that of the WO3/TiO2 film. The results of PEC performance demonstrate that the introduction of WO3-x nanoparticles can improve the charge transfer performance so as to enhance the performance of PEC reduction of CO2 into formic acid.展开更多
Series of TiO 2-ZnO heterojunction composite films with different n（Zn）/n（Ti） ratios were prepared by UDP450 magnetron sputter ion plating equipment, and the mole ratio of Zn to Ti was controlled by adjusting the ...Series of TiO 2-ZnO heterojunction composite films with different n（Zn）/n（Ti） ratios were prepared by UDP450 magnetron sputter ion plating equipment, and the mole ratio of Zn to Ti was controlled by adjusting the current values of sputtering target. The effects of n（Zn）/n（Ti） on the microstructures of TiO2-ZnO films were investigated by SEM, AFM, Raman and XPS, and their photocatalytic decomposition of methyl orange solutions was evaluated. The results show that an increase in n（Zn）/n（Ti） typically results in a decrease in the grain size of composite films firstly and then an increase of grain size, while an increase in n（Zn）/n（Ti） leads to an increase in film roughness firstly and then a decrease in film roughness. Both grain size and roughness of TiO2-ZnO films reach the maximum and minimum at n（Zn）/n（Ti） of 1/9.3, respectively. The n（Zn）/n（Ti） shows little effect on the valences of Zn and Ti elements, which mainly exist in the form of TiO2 and ZnO phases. The n（Zn）/n（Ti） has influence on the amount of anatase/rutile TiO2 heterojunction in the film. With increase of the n（Zn）/n（Ti）, the absorption intensity of the composite film increases and the absorption region extends to 450 nm, which is redshifted as much as 150 nm in comparison with the pure TiO2 films. However, the photocatalytic abilities of heterogeneous composite films do not depend on the n（Zn）/n（Ti） but rather on the microstructures of the TiO2-ZnO composite films. Degradation rate of the film reaches the maximum and the photocatalytic decomposition of pollutants works best when n（Zn）/n（Ti）=1：9.3.展开更多
This paper reported that the Mn-doped TiO2 films were prepared by radio frequency （RF） magnetron cosputtering. X-ray diffraction measurements indicate that the samples are easy to form the futile structure, and the ...This paper reported that the Mn-doped TiO2 films were prepared by radio frequency （RF） magnetron cosputtering. X-ray diffraction measurements indicate that the samples are easy to form the futile structure, and the sizes of the crystal grains grow big and big as the Mn concentration increases. X-ray photoemlssion spectroscopy measurements and high resolution transmission electron microscope photographs confirm that the manganese ions have been effectively doped into the TiO2 crystal when the Mn concentration is lower than 21%. The magnetic property measurements show that the Ti1-xMnxO2 （x = 0.21） films are ferromagnetic at room temperature, and the saturation magnetization, coercivity, and saturation field are 16.0 emu/cm^3, 167.5 × 80 A/m and 3740 × 80 A/m at room temperature, respectively. The room-temperature ferromagnetism of the films can be attributed to the new futile Ti1-xMnxO2 structure formed by the substitution of Mn^4＋ for Ti^4＋ into the TiO2 crystal .lattice, and could be explained by O vacancy （Vo）-enhanced ferromagnetism model.展开更多
A novel titanium dioxide （TiO2） film comprising both nanotubes and nanopaticles was fabricated by an anodization process of the modified titanium. The local electric field at the anodized surface was simulated and i...A novel titanium dioxide （TiO2） film comprising both nanotubes and nanopaticles was fabricated by an anodization process of the modified titanium. The local electric field at the anodized surface was simulated and its influence on the morphology of the TiO2 film was discussed. The results show that the electric field strength is enhanced by the covering. The growth rate of TiO2 increases with the assist of the local electric field. However, TiO2 dissolution is hindered since the local electric field prevents [TiF6]6- from diffusing. It means that the balance condition for the formation of nanotubes is broken, and TiO2 nanoparticles are formed. Moreover, the crystal structure of the TiO2 film was confirmed using X-ray diffraction and Raman analysis. The anatase is a main phase for the proposed film.展开更多
Anatase TiO2 films were successfully prepared on foam nickel substrates by sol-gel technique using tetrabutyl titanate as precursor. The characteristics of the TiO2 films were investigated by XPS, XRD, FE-SEM, TEM and...Anatase TiO2 films were successfully prepared on foam nickel substrates by sol-gel technique using tetrabutyl titanate as precursor. The characteristics of the TiO2 films were investigated by XPS, XRD, FE-SEM, TEM and UV-Vis absorption spectra. The photocatalytic activities of TiO2 films were investigated by photocatalytic degradation reactions of gaseous acetaldehyde, an indoor pollutant, under ultraviolet light irradiation. It was found that Ni^2＋ doping into TiO2 films due to the foam nickel substrates resulted in the extension of absorption edges of TiO2 films from UV region to visible light region. The pre-heating for foam nickel substrates resulted in the formation of NiO layer, which prevented effectively the injection of photogenerated electrons from TiO2 films to metal nickel. The TiO2 films displayed high photocatalytic activity for the degradation of acetaldehyde, and were enhanced by calcining the substrates and coating TiO2 films repeatedly. The high activity was mainly attributed to the improvement of the characteristics of substrate surface and the increase of active sites on photocatalyst.展开更多
TiO2 films were deposited at room temperature by DC pulse magnetron sputtering system.The crystalline structures,morphological features and photocatalytic activity of TiO2 films were systematically investigated by X-r...TiO2 films were deposited at room temperature by DC pulse magnetron sputtering system.The crystalline structures,morphological features and photocatalytic activity of TiO2 films were systematically investigated by X-ray diffraction（XRD）,atomic force microscopy（AFM） and ultraviolet spectrophotometer,respectively.The results indicated that working pressure was the key deposition parameter in？uencing the TiO2 film phase composition at room temperature,which directly affected its photocatalytic activity.With increasing working pressure,the target self-bias decreases monotonously.Therefore,low temperature TiO2 phase（anatase） could be deposited with high working pressure.The anatase TiO2 films deposited with 1.4 Pa working pressure displayed the highest photocatalytic activity by the decomposition of Methyl Orange solution,which the degradation rate reached the maximum（35%） after irradiation by ultraviolet light for 1 h.展开更多
With rapid progressive application of TiO2 thin films, magnetron sputtering becomes a very interesting method to prepare such multi-functional thin films. This paper focuses on influences of various deposition process...With rapid progressive application of TiO2 thin films, magnetron sputtering becomes a very interesting method to prepare such multi-functional thin films. This paper focuses on influences of various deposition processes and deposition rate on the structures and properties of TiO2 thin films. Anatase, rutile or amorphous TiO2 films with various crystalline structures and different photocatalytic, optical and electrical properties can be produced by varying sputtering gases, substrate temperature, annealing process, deposition rate and the characteristics of magnetron sputtering. This may in turn affect the functions of TiO2 films in many applications. Furthermore, TiO2-based composites films can overcome many limitations and improve the properties of TiO2 films.展开更多
The Ni-P/TiO2 composite film on sintered NdFeB permanent magnet was investigated by X-ray diffraction （XRD）,environmental scanning electron microscopy （ESEM）,and energy dispersive X-ray spectrometer （EDX）. The c...The Ni-P/TiO2 composite film on sintered NdFeB permanent magnet was investigated by X-ray diffraction （XRD）,environmental scanning electron microscopy （ESEM）,and energy dispersive X-ray spectrometer （EDX）. The corrosion resistance of Ni-P/TiO2 film coated on NdFeB magnet,in 0.5 mol/L NaCl solution,was studied by potentiodynamic polarization,salt spray test and electrochemical impedance spectroscopy （EIS） techniques. The self-corrosion current density （icorr） and the polarization resistance （Rp） of Ni-P/TiO2 film are 0.22 μA/cm2 （about 14% of that of Ni-P coating）,and 120 kΩ·cm2 （about 2 times of that of Ni-P coating）,respectively. The anti-salt spray time of Ni-P/TiO2 film is about 2.5 times of that of the Ni-P coating. The results indicate that Ni-P/TiO2 film has a better corrosion resistance than Ni-P coating,and the composite film increases the corrosion resistance of NdFeB magnet markedly.展开更多
A novel multi-tube photoreactor with 0.0188m3 valid reaction volume was constructed in pilot-scale. This rectangular reactor consisted of 13 regularly distributed silica glass tubes coating with TiO2 thin film photo-c...A novel multi-tube photoreactor with 0.0188m3 valid reaction volume was constructed in pilot-scale. This rectangular reactor consisted of 13 regularly distributed silica glass tubes coating with TiO2 thin film photo-catalyst. Total active area of TiO2 thin film is 0.3916m2. The ratio of surface area to volume achieves 20.8m-1. Photocatalytic experiment of phenol red demonstrates that the apparent reaction rate constant (k) is 0.074 65 h-1 and 0.16502h-1 for reaction system with and without micro-bubbles mixing. The corresponding apparent quantum efficiency (a) is 8.1771 X 10-7g.J-1 and 4.9036 x 10-7g-J-1, respectively. COD value of reactant could decrease to 17mg.L-1 and high performance liquid chromatography (HPLC) only shows two absorption peaks in 24 h pho-tocatalytic process time, so this photoreactor has good photomineralization effect. Experimental results reveal that photocatalytic destruction of organics is possible by using the multi-tube photoreactor.展开更多
We synthesized a mesoporous film based on TiO2-reduced graphene oxide(RGO)hybrids using a one-step vapor-thermal method without the need for an additional annealing process.The vapor-thermally prepared TiO2-graphene h...We synthesized a mesoporous film based on TiO2-reduced graphene oxide(RGO)hybrids using a one-step vapor-thermal method without the need for an additional annealing process.The vapor-thermally prepared TiO2-graphene hybrid(VTH)features unique structures with an ultra-large specific surface area of^260 m^2 g^-1 and low aggregation,giving rise to enhanced light harvesting and increased charge generation and separation efficiency.It was observed that a mesoporous film with uniform pore distribution is simultaneously obtained during the VTH growth process.When a 5.0 wt%RGO VTH film was used as the active layer in photocatalysis,the highest photocatalytic activity for degradation of methyl orange was achieved.For another,when a 0.75 wt%RGO VTH film was used as the photoanode in a dye-sensitized solar cell,the power conversion efficiency reached 7.58%,which represents an increase of 73.1%compared to a solar cell using an a photoanode of pure TiO2 synthesized by a traditional solvothermal method.It is expected that this facile method for the synthesis of TiO2/graphene hybrid mesoporous films will be useful in practical applications for preparing other metal oxide/graphene hybrids with ultra-high photocatalytic activity and photovoltaic performance.展开更多
TiO2 film modified by Bi2O3 microgrid array was successfully fabricated by using a microsphere lithography method.The structure and morphology of TiO2 film,Bi2O3 film and TiO2 film/Bi2O3 microgrid heterojunction were ...TiO2 film modified by Bi2O3 microgrid array was successfully fabricated by using a microsphere lithography method.The structure and morphology of TiO2 film,Bi2O3 film and TiO2 film/Bi2O3 microgrid heterojunction were characterized through X-ray diffraction,atomic force microscopy and scanning electron microscopy.The optical transmittance spectra and the photocatalytic degradation capacity of these samples to rhodamine B were determined via ultraviolet-visible spectroscopy.The results indicated that the coupled system showed higher photocatalytic activity than pure TiO2 and Bi2O3 films under xenon lamp irradiation.The enhancement of the photocatalytic activity was ascribed to the special structure,which could improve the separation of photo-generated electrons and holes,enlarge the surface area and extend the response range of TiO2 film from ultraviolet to visible region.展开更多
基金Project(cstc2011jj A50008)supported by the Natural Science Foundation of Chongqing,ChinaProject(14ZB0025)supported by Education Department of Sichuan Province,China
文摘Zn-doped TiO2 (Zn?TiO2) thin films were prepared by the sol?gel method on titanium substrates with heat treatment at different temperatures. The effects of heat treatment temperatures and Zn doping on the structure, photocathodic protection and photoelectrochemical properties of TiO2 thin films were investigated. It is indicated that the photoelectrical performance of the Zn?TiO2 films is enhanced with the addition of Zn element compared with the pure-TiO2 film and the largest decline by 897 mV in the electrode potential is achieved under 300 °C heat treatment. SEM?EDS analyses show that Zn element is unevenly distributed in Zn?TiO2 films; XRD patterns reveal that the grain size of Zn?TiO2 is smaller than that of pure-TiO2; FTIR results indicate that Zn - O bond forms on Zn?TiO2 surface. Ultraviolet visible absorption spectra prove that Zn?TiO2 shifts to visible light region.Mott?Shottky curves show that the flat-band potential of Zn?TiO2 is more negative and charge carrier density is bigger than that ofpure-TiO2, implying that under the synergy of the width of the space-charge layer, carrier density and flat-band potential, Zn?TiO2 with 300 °C heat treatment displays the best photocathodic protection performance.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.20773113）, the Solar Energy Project of Chinese Academy of Sciences, the Ministry of Education program for PCSIRT （No.IRT0756）, and the Max Planck Gesellschaft of Chinese Academy of Sciences partner group.
文摘We developed a novel approach for the preparation of N-doped TiO2 photocatalysts by calcining ammonium titanium oxalate at different temperatures. The structures of N-TiO2 were characterized by powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, diffuse reflectance UV-Vis spectroscopy, and scanning electron microscope. The N-doped TiO2 photocatalysts calcined below 700 ℃ are the pure anatase phase but that calcined at 700 ℃ is a mixture of anatase and rutile phases. The doped N locates at the interstitial site of TiO2 which leads to the narrowing of bad gap of pure anatase N-TiO2. Among all photocatalysts, N-TiO2 photocatalysts calcined at 600 and 400 ℃ exhibit the best performance in the photodegradation of methyl orange under the UV light and all-wavelength light illuminations, respectively; however, because of the perfect crystallinity and the existence of anatase-rutile phase junctions, N-TiO2 photocatalyst calcined at 700 ℃ exhibits the highest specific photodegradation rate, i.e., the highest quantum yield, under both the UV light and all-wavelength light illuminations.
基金financially supported by National Natural Science Foundation of China (Grant No.51772213)973 Program (Grant No. 2013CB632701)
文摘In this paper, SnS_2 nanosheets arrays sandwiched by porous N-doped carbon and TiO_2(TiO_2@SnS_2@N-C) on flexible carbon cloth are prepared and tested as a free-standing anode for high-performance sodium ion batteries. The as-obtained TiO_2@SnS_2@N-C composite delivers a remarkable capacity performance(840 mA h g^(-1) at a current density of 200 mA g^(-1)), excellent rate capability and long-cycling life stability(293 mA h g^(-1) at 1 A g^(-1) after 600 cycles). The excellent electrochemical performance can be attributed to the synergistic effect of each component of the unique hybrid structure, in which the SnS_2 nanosheets with open framworks offer high capacity, while the porous N-doped carbon nanoplates arrays on flexible carbon cloth are able to improve the conductivity and the TiO_2 passivation layer can keep the structure integrity of SnS_2 nanosheets.
基金This work was supported financially by the National Natural Science Foundation of China(No.51602044)the Fundamental Research Funds for the Central Universities(No.N170205021)。
文摘Lithium-sulfur batteries hold promise for next generation batteries due to their high theoretical energy density and low cost.However,the rapid capacity fading caused by the shuttle of polysulfide between two electrodes severely hinders the practical application of Li-S batteries.To address the issue,we reported a three-dimensional heterostructured TiO2 nanosheets/N-doped carbon(TO/NC),which is coated on a commercial polypro pylene(PP) separator,as an efficient barrier for Li-S batteries.The TO/NC coating layer provides a bipolar chemical adsorption of lithium polysulfides(LiPSs) via TiO2 nanosheets with exposed(001) facets and N-doped carbon,showing high trapping capacity and remarkable electrocatalytic activity for LiPSs.The slurry-bladed carbon black/sulfur cathode with 64 wt% sulfur offers outstanding performance with an initial capacity of 1314 mAh g^-1 at 0.2 C.Over 900 cycles,the cell still maintains the capacity of 448 mA h g^-1 at a 1 C rate with a degradation rate of only 0.055% per cycle.The separator reported in this work holds great promise for the development of high-energy Li-S batteries.
基金Supported by the National Natural Science Foundation of China (No. 20503021)National Basic Research Program of China (2007CB815301)
文摘A systematic study on geometry, electronic structure and vibrational properties of N-doped TiO2 anatase cluster, within the framework of the density functional theory, has been performed in this work. The calculations confirmed that the most structures in substitutional model consist of a two-coordinate bridge structure and a three-coordinate hollow structure. The calculated results can well explain the red shift in N-doped TiO2 observed in experiments. The study provides an illustration for the N-doped anatase from the viewpoint of chemical bonding theory.
文摘A novel visible light-active photocatalyst formulation（NdT/OP） was obtained by supporting N-doped TiO2（NdT） particles on up-conversion luminescent organic phosphors（OP）. The photocatalytic activity of such catalysts was evaluated for the mineralization process of spiramycin in aqueous solution. The effect of NdT loading in the range 15–60 wt.% on bulk and surface characteristics of NdT/OP catalysts was investigated by several chemicophysical characterization techniques. The photocatalytic performance of NdT/OP catalysts in the removal of spyramicin from aqueous solution was assessed through photocatalytic tests under visible light irradiation. Total organic carbon（TOC） of aqueous solution,and CO and CO2 gas concentrations evolved during the photodegradation were analyzed. A dramatic enhancement of photocatalytic activity of the photostructured visible active NdT/OP catalysts,compared to NdT catalyst,was observed. Only CO2 was detected in gas-phase during visible light irradiation,proving that the photocatalytic process is effective in the mineralization of spiramycin,reaching very high values of TOC removal. The photocatalyst NdT/OP at 30 wt.% of NdT loading showed the highest photocatalytic activity（58%of TOC removed after 180 min irradiation against only 31% removal after 300 min of irradiation of NdT）. We attribute this enhanced activity to the high effectiveness in the utilization of visible light through improved light harvesting and exploiting. OP particles act as ＂photoactive support＂,able to be excited by the external visible light irradiation,and reissue luminescence of wavelength suitable to promote NdT photomineralization activity.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.62205231 and 22002102)the Postgraduate Research&Practice Innovation Program of Jiangsu Province,China(Grant No.KYCX223271)Jiangsu Key Laboratory for Environment Functional Materials。
文摘Multilevel phase-change memory is an attractive technology to increase storage capacity and density owing to its high-speed,scalable and non-volatile characteristics.However,the contradiction between thermal stability and operation speed is one of key factors to restrain the development of phase-change memory.Here,N-doped Ge_(2)Sb_(2)Te_(5)-based optoelectronic hybrid memory is proposed to simultaneously implement high thermal stability and ultrafast operation speed.The picosecond laser is adopted to write/erase information based on reversible phase transition characteristics whereas the resistance is detected to perform information readout.Results show that when N content is 27.4 at.%,N-doped Ge_(2)Sb_(2)Te_(5)film possesses high ten-year data retention temperature of 175℃and low resistance drift coefficient of 0.00024 at 85℃,0.00170 at 120℃,and 0.00249 at 150℃,respectively,owing to the formation of Ge–N,Sb–N,and Te–N bonds.The SET/RESET operation speeds of the film reach 520 ps/13 ps.In parallel,the reversible switching cycle of the corresponding device is realized with the resistance ratio of three orders of magnitude.Four-level reversible resistance states induced by various crystallization degrees are also obtained together with low resistance drift coefficients.Therefore,the N-doped Ge_(2)Sb_(2)Te_(5)thin film is a promising phase-change material for ultrafast multilevel optoelectronic hybrid storage.
基金supported financially by the National Natural Science Foundation of China(Grant No.51272107 and Grant No.51572126)the Department of Education of Jiangsu Province(KYLX_0352)Fundamental Research Funds for the Central Universities(No.30920140132038)
文摘In this paper, ultrafine nitrogen-doped TiO2 photocatalyst with enhanced photocatalytic water-splitting properties was successfully fabricated via a solvothermal method. Herein, polyvinylpyrrolidone（PVP） was used as both nitrogen source and stabilizer. The enhancement in water-splitting process can be attributed to the doping of element nitrogen, which could supply an intermediate energy level and promote the separation of photo-excited holes and electrons. Moreover, this paper provides a new application of high-molecular polymer to synthesize solar-driven water-splitting photocatalysts.
基金Project(gf200901002)supported by the Open Research Fund of National Defense Key Disciplines Laboratory of Light Alloy Processing Science and Technology of Nanchang Hangkong University,China
文摘ZrO2/TiO2 composite photocatalytic film was produced on the pure titanium substrate using in-situ Zr（OH）4 colloidal particle by the micro-arc oxidation technique and characterized by scanning electron microscope （SEM）, energy dispersive X-ray （EDX）, X-ray diffraction （XRD） and ultraviolet-visible （UV-Vis） spectrophotometer. The composite film shows a lamellar and porous structure which consists of anatase, futile and ZrO2 phases. The optical absorption edge of film is shifted to longer wavelength when ZrO2 is introduced to TiO2. Furthermore, the photocatalytic reaction rate constants of degradation of rhodamine B solution with ZrO2/TiO2 composite film and pure TiO2 film under ultraviolet irradiation are measured as 0.0442 and 0.0186 h 1, respectively.
基金Project(21471054)supported by the National Natural Science Foundation of China
文摘A novel WO3-x/TiO2 film as photoanode was synthesized for photoelectrocatalytic（PEC） reduction of CO2 into formic acid（HCOOH）. The films prepared by doctor blade method were characterized with X-ray diffractometer（XRD）, scanning electron microscope（SEM） and transmission electron microscope（TEM）. The existence of oxygen vacancies in the WO3-x was confirmed with an X-ray photoelectron spectroscopy（XPS）, and the accurate oxygen index was determined by a modified potentiometric titrimetry method. After 3h of photoelectrocatalytic reduction, the formic acid yield of the WO3-x/TiO2 film is 872 nmol/cm^2, which is 1.83 times that of the WO3/TiO2 film. The results of PEC performance demonstrate that the introduction of WO3-x nanoparticles can improve the charge transfer performance so as to enhance the performance of PEC reduction of CO2 into formic acid.
基金Project (2010JQ6008) supported by the Natural Science Foundation of Shaanxi Province,China
文摘Series of TiO 2-ZnO heterojunction composite films with different n（Zn）/n（Ti） ratios were prepared by UDP450 magnetron sputter ion plating equipment, and the mole ratio of Zn to Ti was controlled by adjusting the current values of sputtering target. The effects of n（Zn）/n（Ti） on the microstructures of TiO2-ZnO films were investigated by SEM, AFM, Raman and XPS, and their photocatalytic decomposition of methyl orange solutions was evaluated. The results show that an increase in n（Zn）/n（Ti） typically results in a decrease in the grain size of composite films firstly and then an increase of grain size, while an increase in n（Zn）/n（Ti） leads to an increase in film roughness firstly and then a decrease in film roughness. Both grain size and roughness of TiO2-ZnO films reach the maximum and minimum at n（Zn）/n（Ti） of 1/9.3, respectively. The n（Zn）/n（Ti） shows little effect on the valences of Zn and Ti elements, which mainly exist in the form of TiO2 and ZnO phases. The n（Zn）/n（Ti） has influence on the amount of anatase/rutile TiO2 heterojunction in the film. With increase of the n（Zn）/n（Ti）, the absorption intensity of the composite film increases and the absorption region extends to 450 nm, which is redshifted as much as 150 nm in comparison with the pure TiO2 films. However, the photocatalytic abilities of heterogeneous composite films do not depend on the n（Zn）/n（Ti） but rather on the microstructures of the TiO2-ZnO composite films. Degradation rate of the film reaches the maximum and the photocatalytic decomposition of pollutants works best when n（Zn）/n（Ti）=1：9.3.
基金Project supported by the Aeronautical Science foundation of China (Grant No 2003ZG51069)the National Defence BaseResearch of China
文摘This paper reported that the Mn-doped TiO2 films were prepared by radio frequency （RF） magnetron cosputtering. X-ray diffraction measurements indicate that the samples are easy to form the futile structure, and the sizes of the crystal grains grow big and big as the Mn concentration increases. X-ray photoemlssion spectroscopy measurements and high resolution transmission electron microscope photographs confirm that the manganese ions have been effectively doped into the TiO2 crystal when the Mn concentration is lower than 21%. The magnetic property measurements show that the Ti1-xMnxO2 （x = 0.21） films are ferromagnetic at room temperature, and the saturation magnetization, coercivity, and saturation field are 16.0 emu/cm^3, 167.5 × 80 A/m and 3740 × 80 A/m at room temperature, respectively. The room-temperature ferromagnetism of the films can be attributed to the new futile Ti1-xMnxO2 structure formed by the substitution of Mn^4＋ for Ti^4＋ into the TiO2 crystal .lattice, and could be explained by O vacancy （Vo）-enhanced ferromagnetism model.
文摘A novel titanium dioxide （TiO2） film comprising both nanotubes and nanopaticles was fabricated by an anodization process of the modified titanium. The local electric field at the anodized surface was simulated and its influence on the morphology of the TiO2 film was discussed. The results show that the electric field strength is enhanced by the covering. The growth rate of TiO2 increases with the assist of the local electric field. However, TiO2 dissolution is hindered since the local electric field prevents [TiF6]6- from diffusing. It means that the balance condition for the formation of nanotubes is broken, and TiO2 nanoparticles are formed. Moreover, the crystal structure of the TiO2 film was confirmed using X-ray diffraction and Raman analysis. The anatase is a main phase for the proposed film.
基金Project supported by the Special Foundation of Nanometer Technology from Shanghai Municipal Science and Technology Commis-sion(STCSM) (No. 0552nm002).
文摘Anatase TiO2 films were successfully prepared on foam nickel substrates by sol-gel technique using tetrabutyl titanate as precursor. The characteristics of the TiO2 films were investigated by XPS, XRD, FE-SEM, TEM and UV-Vis absorption spectra. The photocatalytic activities of TiO2 films were investigated by photocatalytic degradation reactions of gaseous acetaldehyde, an indoor pollutant, under ultraviolet light irradiation. It was found that Ni^2＋ doping into TiO2 films due to the foam nickel substrates resulted in the extension of absorption edges of TiO2 films from UV region to visible light region. The pre-heating for foam nickel substrates resulted in the formation of NiO layer, which prevented effectively the injection of photogenerated electrons from TiO2 films to metal nickel. The TiO2 films displayed high photocatalytic activity for the degradation of acetaldehyde, and were enhanced by calcining the substrates and coating TiO2 films repeatedly. The high activity was mainly attributed to the improvement of the characteristics of substrate surface and the increase of active sites on photocatalyst.
基金supported by the Dalian Foundation for Development of Science and Technology (No.2006A13GX029)
文摘TiO2 films were deposited at room temperature by DC pulse magnetron sputtering system.The crystalline structures,morphological features and photocatalytic activity of TiO2 films were systematically investigated by X-ray diffraction（XRD）,atomic force microscopy（AFM） and ultraviolet spectrophotometer,respectively.The results indicated that working pressure was the key deposition parameter in？uencing the TiO2 film phase composition at room temperature,which directly affected its photocatalytic activity.With increasing working pressure,the target self-bias decreases monotonously.Therefore,low temperature TiO2 phase（anatase） could be deposited with high working pressure.The anatase TiO2 films deposited with 1.4 Pa working pressure displayed the highest photocatalytic activity by the decomposition of Methyl Orange solution,which the degradation rate reached the maximum（35%） after irradiation by ultraviolet light for 1 h.
文摘With rapid progressive application of TiO2 thin films, magnetron sputtering becomes a very interesting method to prepare such multi-functional thin films. This paper focuses on influences of various deposition processes and deposition rate on the structures and properties of TiO2 thin films. Anatase, rutile or amorphous TiO2 films with various crystalline structures and different photocatalytic, optical and electrical properties can be produced by varying sputtering gases, substrate temperature, annealing process, deposition rate and the characteristics of magnetron sputtering. This may in turn affect the functions of TiO2 films in many applications. Furthermore, TiO2-based composites films can overcome many limitations and improve the properties of TiO2 films.
基金Sponsored by Hi-Tech Research and Development Program of China (2003AA305120)
文摘The Ni-P/TiO2 composite film on sintered NdFeB permanent magnet was investigated by X-ray diffraction （XRD）,environmental scanning electron microscopy （ESEM）,and energy dispersive X-ray spectrometer （EDX）. The corrosion resistance of Ni-P/TiO2 film coated on NdFeB magnet,in 0.5 mol/L NaCl solution,was studied by potentiodynamic polarization,salt spray test and electrochemical impedance spectroscopy （EIS） techniques. The self-corrosion current density （icorr） and the polarization resistance （Rp） of Ni-P/TiO2 film are 0.22 μA/cm2 （about 14% of that of Ni-P coating）,and 120 kΩ·cm2 （about 2 times of that of Ni-P coating）,respectively. The anti-salt spray time of Ni-P/TiO2 film is about 2.5 times of that of the Ni-P coating. The results indicate that Ni-P/TiO2 film has a better corrosion resistance than Ni-P coating,and the composite film increases the corrosion resistance of NdFeB magnet markedly.
基金Supported by the Natural Science Foundation of Jiangsu Province (JH01-010).
文摘A novel multi-tube photoreactor with 0.0188m3 valid reaction volume was constructed in pilot-scale. This rectangular reactor consisted of 13 regularly distributed silica glass tubes coating with TiO2 thin film photo-catalyst. Total active area of TiO2 thin film is 0.3916m2. The ratio of surface area to volume achieves 20.8m-1. Photocatalytic experiment of phenol red demonstrates that the apparent reaction rate constant (k) is 0.074 65 h-1 and 0.16502h-1 for reaction system with and without micro-bubbles mixing. The corresponding apparent quantum efficiency (a) is 8.1771 X 10-7g.J-1 and 4.9036 x 10-7g-J-1, respectively. COD value of reactant could decrease to 17mg.L-1 and high performance liquid chromatography (HPLC) only shows two absorption peaks in 24 h pho-tocatalytic process time, so this photoreactor has good photomineralization effect. Experimental results reveal that photocatalytic destruction of organics is possible by using the multi-tube photoreactor.
文摘We synthesized a mesoporous film based on TiO2-reduced graphene oxide(RGO)hybrids using a one-step vapor-thermal method without the need for an additional annealing process.The vapor-thermally prepared TiO2-graphene hybrid(VTH)features unique structures with an ultra-large specific surface area of^260 m^2 g^-1 and low aggregation,giving rise to enhanced light harvesting and increased charge generation and separation efficiency.It was observed that a mesoporous film with uniform pore distribution is simultaneously obtained during the VTH growth process.When a 5.0 wt%RGO VTH film was used as the active layer in photocatalysis,the highest photocatalytic activity for degradation of methyl orange was achieved.For another,when a 0.75 wt%RGO VTH film was used as the photoanode in a dye-sensitized solar cell,the power conversion efficiency reached 7.58%,which represents an increase of 73.1%compared to a solar cell using an a photoanode of pure TiO2 synthesized by a traditional solvothermal method.It is expected that this facile method for the synthesis of TiO2/graphene hybrid mesoporous films will be useful in practical applications for preparing other metal oxide/graphene hybrids with ultra-high photocatalytic activity and photovoltaic performance.
基金supported by the National High Technology Research and Development Program of China under Grant 2009AA03Z428the National Natural Science Foundation of China under Grant No. 50872005the National Basic Research Program of China under Grant 2007CB613306
文摘TiO2 film modified by Bi2O3 microgrid array was successfully fabricated by using a microsphere lithography method.The structure and morphology of TiO2 film,Bi2O3 film and TiO2 film/Bi2O3 microgrid heterojunction were characterized through X-ray diffraction,atomic force microscopy and scanning electron microscopy.The optical transmittance spectra and the photocatalytic degradation capacity of these samples to rhodamine B were determined via ultraviolet-visible spectroscopy.The results indicated that the coupled system showed higher photocatalytic activity than pure TiO2 and Bi2O3 films under xenon lamp irradiation.The enhancement of the photocatalytic activity was ascribed to the special structure,which could improve the separation of photo-generated electrons and holes,enlarge the surface area and extend the response range of TiO2 film from ultraviolet to visible region.
